Citric Acid → 7-[2-Hydroxy-5-(3-hydroxyoct-1-enyl)-3-(2-tetrahydropyranyloxy)cyclopentyl]heptanoic acid

HRID 442445Notes

Reaction equation

HRID 442445 reaction equation
[O:1]=[C:2]1[CH:6]([O:7][CH:8]2[CH2:13][CH2:12][CH2:11][CH2:10][O:9]2)[CH2:5][CH:4]([CH:14]=[CH:15][C:16](=[O:22])[CH2:17][CH2:18][CH2:19][CH2:20][CH3:21])[CH:3]1[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][C:29]([OH:31])=[O:30].C([O-])(=O)CC(CC([O-])=O)(C([O-])=O)O.[Na+].[Na+].[Na+].[BH4-].[K+].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CO.CC(C)=O>[OH:1][CH:2]1[CH:6]([O:7][CH:8]2[CH2:13][CH2:12][CH2:11][CH2:10][O:9]2)[CH2:5][CH:4]([CH:14]=[CH:15][CH:16]([OH:22])[CH2:17][CH2:18][CH2:19][CH2:20][CH3:21])[CH:3]1[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][C:29]([OH:31])=[O:30]

Participants

7

Reactant 4

HCID 311Citric Acid3×HCID 6224Trisodium citrateHCID 4192641Potassium borohydride2×HCID 867329967-(2-Oxo-5-(3-oxooct-1-enyl)-3-(2-tetrahydropyranyloxy)cyclopentyl]heptanoic acid

Product 1

HCID 543618807-[2-Hydroxy-5-(3-hydroxyoct-1-enyl)-3-(2-tetrahydropyranyloxy)cyclopentyl]heptanoic acidYield 74.9%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 887MethanolSolvent

Procedure

A solution of 7-[2-oxo-5-(3-oxooct-1-enyl)-3-(2-tetrahydropyranyloxy)cyclopentyl]heptanoic acid [0.45 g.; prepared as described above in Example 2(g)] in methanol (10 ml.) was added to a stirred 2% w/v aqueous solution of sodium citrate (100 ml.) at -5° C. Potassium borohydride (1.6 g.) was then added portionwise, allowing the pH to change to pH 8 and then maintaining at pH 8 by the addition, when necessary, of quantities of 10% w/v aqueous citric acid solution. When the addition of the potassium borohydride was complete, the solution was stirred for 90 minutes, meanwhile maintaining the pH at pH 8 by means of the addition of further quantities of the citric acid solution, and allowing it to attain room temperature. The solution was then treated with acetone (50 ml.), treated with a further quantity of the citric acid solution to bring the pH to pH 4, saturated with sodium chloride and extracted 3 times with diethyl ether. The combined ethereal extracts were washed with a saturated solution of sodium chloride in 2N hydrochloric acid, and then with a saturated aqueous solution of sodium chloride, and dried over magnesium sulphate. The solvent was removed in vacuo to give crude 7-[2-hydroxy-5-(3-hydroxyoct-1-enyl)-3-(2-tetrahydropyranyloxy)cyclopentyl]heptanoic acid (0.34 g.), νmax 1700 cm-1, 980 cm-1 , which was used as starting material in the following preparation (i) of 7-[2,3-dihydroxy-5-(3-hydroxyoct-1-enyl)cyclopentyl]heptanoic acid without further purification being necessary.

Workup

  1. customat -5° C
  2. temperaturemaintaining at pH 8 by the addition, when necessary
  3. temperaturemeanwhile maintaining the pH at pH 8
  4. customto attain room temperature
  5. extractionsaturated with sodium chloride and extracted 3 times with diethyl ether
  6. washThe combined ethereal extracts were washed with a saturated solution of sodium chloride in 2N hydrochloric acid
  7. dry with materialwith a saturated aqueous solution of sodium chloride, and dried over magnesium sulphate
  8. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-84df1ab9a82b4b638a1ee72389189447
Source dataset
uspto-grants-1977_08
Patent number
US04045467

Reaction notes

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